JPH08259739A - Silica-reinforced rubber composition and its use for tire - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the rubber compsn. reinforced by a combination with a silica-bonding agent by mixing an elastomer, silica, a particulate filler, an organosilane polysulfide, a sulfur source, a vulcanization accelerator, and additional ingredients.

SOLUTION: 100 pts.wt. sulfur-vulcanizable elastomer selected for among a conjugated diene homo- or copolymer and a conjugated diene-arom. vinyl compd. copolymer is mixed with 15-100 phr. at least one particulate filler selected from among precipitated silica, alumina, an aluminosilicate, and a carbon black, an organosilane polysulfide of formula: Z-R¹-S_n-R¹-Z [wherein n is 2-8; and Z is a group represented by formula I (wherein R² is 1-4C alkyl or phenyl; and R³ is 1-4C alkyl, phenyl, 1-8C alkoxy, or 5-8C cycloalkoxy)] in an amt. of 0.05-20 pts.wt. based on 1 pt.wt. particulate filler, a sulfur source (e.g. an elemental sulfur or a polysulfide) in an amt. of 0.05-2 phr (in terms of free sulfur), 0.1-0.5 phr vulcanization accelerator, and additional ingredients.

COPYRIGHT: (C)1996,JPO

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to the preparation of rubber compositions containing silica reinforcement and the use of silica coupling agents or adhesives in the form of relatively pure organosilane disulfides.

The invention also relates to the manufacture of tires with treads. In one embodiment, the rubber composition is reinforced with a combination of silica, alumina and / or aluminosilicate, optionally carbon black, and a silica coupling agent or adhesive in the form of relatively pure organosilane disulfide. It is made of vulcanizable (vulcanizable) rubber.

[0003]

Vulcanized rubbers containing a significant amount of reinforcing fillers are used in various applications utilizing rubbers requiring high strength and abrasion resistance, especially in applications such as tires and various industrial products. To be Carbon black is commonly used for such purposes and usually provides or enhances good physical properties in the vulcanized rubber.
Granular precipitated silica is sometimes used for such purposes, especially when silica is used with a coupling agent. In some cases, a combination of silica and carbon black is used as a reinforcing filler for various rubber products, including tire treads.

In some cases, alumina has been used for such purposes alone or in combination with silica. The term "alumina" is silica oxide, i.e. in this case the Al ₂ O ₃ can be described.
The use of alumina in rubber compositions is described, for example, in US Pat. No. 5,116,886 and European Patent Publication E.
PO 631,982 A2.

It is recognized that alumina can be in various forms, such as acidic, neutral and basic forms. In general, the neutral form is considered preferred here.

In some cases, aluminosilicates may be used for such purpose. The term "aluminosilicate" can be described as a natural or synthetic material in which the silicon atoms of silicon dioxide have been partially or naturally replaced by aluminum atoms, ie substituted. For example, about 5 silicon atoms in silicon dioxide
About 90%, or about 10% to about 80%, is naturally or synthetically replaced by aluminum atoms, i.e., when substituted, becomes an aluminosilicate. Suitable methods for such production are, for example, by co-precipitation by adjusting the pH of a basic solution or mixture of silicates and aluminates, and also for example SiO ₂ , or silanols on the surface of silicon dioxide and NaAlO ₂ . Can be explained by the chemical reaction of For example, in such a co-precipitation method, the synthetic co-precipitated aluminosilicate will have about 5-5% of its surface.
About 95% consists of silica parts, and correspondingly about 95 to about 5% of its surface consists of aluminum parts.

Examples of natural aluminosilicates include muscovite,
Beryl, dichroite, sepiolite and kaolinite. Examples of synthetic aluminosilicates are zeolites,
And, for example, the formula [(Al ₂ O ₃ ) _x. (SiO ₂ ) _y. (H _{2
O) z]; [(Al} 2 O 3) x · (SiO 2) y · MO] ( wherein, M is represented by the a is) magnesium or calcium. The use of aluminosilicates in rubber compositions is described, for example, in US Pat. No. 5,116,886,
European Patent Publication EPO 063,982 A
2, Rubber Chem. Tech. , Volume 50,
P. 606 (1988) and vol. 60, p. 84 (198).
3).

Generally, reinforcing fillers for rubber products, especially for rubber tire treads, where carbon black is much more effective than silica unless silica is used in combination with a silica coupler or a coupling agent, also referred to as a silica adhesive compound or coupling agent. It is important to recognize that

Such silica coupling agents or silica adhesives are, for example, premixed or prereacted with silica particles or added to the rubber mixture during the rubber / silica processing or mixing step. It is believed that if the coupling agent and silica are added to the rubber mixture separately during the rubber / silica mixing or processing step, the coupling agent will combine with the silica in situ.

In particular, such coupling agents are sometimes rubbers, especially vulcanizable rubbers, which contain constituents or moieties capable of reacting with the silica surface (silane moieties) and also carbon-carbon double bonds or unsaturations. It comprises an organosilane such as an organosilane polysulfide having a component or moiety capable of reacting with. Thus, the coupling agent then acts as a bond bridge between the silica and the rubber, enhancing the rubber-reinforcing effect of the silica.

A number of coupling agents used in the combination of silica and rubber have been shown, for example silane coupling agents containing a polysulfide component or structure in which the polysulfide bridge portion consists of 2 to 8 sulfur units, such as those from Degussa. There is an organosilane polysulfide, also called bis- (3-triethoxysilylpropyl) tetrasulfide, available as Si69. Such "tetrasulfide" sulfur bridge moieties have an average of about 3.5 to about 4 bonded sulfur atoms, but actually have from about 2 to about 6 or 8 bonded sulfur atoms in the bridge moiety. , 25% or less of the bridge portion is understood to contain two bound sulfur atoms. Therefore,
It is believed herein that at least 75% of the sulfur bridge moieties contain 3 or more bound sulfur atoms. For example, US Pat. No. 4,076,550; 4,704,414.
No. 3,873,489.

Since free sulfur is liberated, for example, at temperatures of about 150 ° C. and above, such organosilane polysulfides containing three or more bound sulfur atoms in the sulfur bridge moiety also can be vulcanized or partially vulcanizable elastomers. It can be seen that it also acts as a sulfur donor for the liberation of free sulfur associated with vulcanization. Above temperatures are approximate temperatures, which are believed herein to depend on the choice of various individual organosilane polysulfides as well as other factors, but at temperatures below about 150 ° C., those sulfur bridge moieties may range from 3 to 3%. For most practical organosilane polysulfides containing 8 sulfur atoms, the liberation of free sulfur, if any, is believed to occur at a relatively slow rate.

Such temperatures are, for example, preliminarily or generally mixed with the rubber and rubber compounding ingredients, excluding free sulfur, sulfur donors and / or rubber vulcanization accelerators, non-productive ( It is empirically understood in the pre-mixing process also called non-productive). Such mixing is
For example, generally at about 140 ° C to about 180 ° C; at least some mixing is most likely at least at 160 ° C or above. A small amount of free sulfur is then used for compounding and / or possibly partial vulcanization with unsaturated elastomers, which is mixed with silica and coupling agents in such a mixing stage.

Bis- (3-triethoxysilylpropyl) disulfide as various organosilane polysulfides is also useful as a silica coupling agent for silica-containing vulcanizable elastomeric compositions, even in highly pure form. However, for example, U.S. Pat. No. 4,046,55
No. 0 and German patent publication DT 2,360,471.
No. However, it is believed herein that such disulfides do not normally liberate free sulfur in the rubber / silica / coupling agent mixing operation described above.

In practice, sulfur vulcanized elastomer products are generally prepared by stepwise thermomechanically mixing rubber and various components, then molding and curing the compounded rubber to form a vulcanized product. Manufactured.

First, for the above-described mixing of rubber and various ingredients, generally excluding sulfur and vulcanization accelerators, the elastomer and various rubber compounding ingredients are mixed in at least one, and usually at least one, in a suitable mixer. Generally mixed in two pre-thermo-mechanical mixing steps. Such premixing is often referred to as nonproductive mixing, or nonproductive mixing steps or stages. Such pre-mixing is about 140 ° C
It is usually done at -190 ° C, often about 150-180 ° C.

After such a pre-mixing stage, in a final mixing stage, also referred to as a productive mixing stage, the sulfur and vulcanization accelerator, and possibly one or more additional ingredients, are added to the rubber compound or composition, generally about. Mix at 100 ° C to about 130 ° C. This temperature is lower than the temperature used in the premixing stage to prevent premature curing of the vulcanizable rubber of the rubber composition, also called scorching.

The rubber mixture, also referred to as a rubber compound or composition, is sometimes cooled to a temperature of about 50 ° C. or less, either after or during the intermediate roll milling step during the various mixing stages described above.

Such sequential non-productive mixing steps and final mixing steps, including intermediate roll kneading and mixing steps, are well known to those having skill in the rubber mixing art.

Thermo-mechanical mixing means that the rubber compound, that is, the composition of the rubber and the rubber compounding components, is mixed within the rubber compound under high shear conditions which results in self-heating, predominantly in the rubber compounding machine. It is meant that the temperature rise is accompanied by mixing due to internal shear and friction.

Such thermo-mechanical rubber compounding methods and the associated shear and temperature increases are well known to those having skill in the rubber manufacturing and mixing arts.

When an organosilane polysulfide (also called an organosilicon polysulfide) is used as the silica coupling agent in a silica reinforced vulcanizable rubber composition, this results in one or more preliminary non-production as pointed out above. Is generally added in the dynamic mixing stage, for example about 140 ° C.
To about 190 ° C, or about 150 ° C to about 180 ° C, generally mixed.

[0023]

Specifically, an organosilane polysulfide containing three or more linked or continuous bridged sulfur units as described above is used, and is
It is believed that at least three chemical reactions take place when the vulcanizable elastomer, silica, and related compounding ingredients are added in the pre-mixing stage described above to mix, for example, from about 140 ° C to about 180 ° C.

It is believed herein that the first reaction is a relatively fast reaction, which occurs between silica and the silane portion of the organosilane, such as the organosilane polysulfide. Such reactions may occur at relatively low temperatures, eg about 120 ° C. Such reactions are well known to those who have experienced silica toughening of vulcanizable elastomers using organosilane polysulfides as silica coupling agents.

The second and third reactions are conducted at higher temperatures, such as above about 140 ° C., between the organosilane polysulfide or polysulfide portion of the coupling agent and the vulcanizable elastomer containing carbon-carbon double bonds. It is considered here to occur at temperatures of. One or more such second and third reactions are well known to those skilled in the art and experience.

The second reaction above is the reaction of the sulfur of the organosilane polysulfide with the carbon of the polymer chain of the elastomer (probably at the alpha carbon atom of the elastomer carbon-
It is believed herein to be consistent with the degree of grafting of the organosilane polysulfide onto the elastomer backbone by covalent bonding (to the carbon double bond). For such a mechanism, see S. Wolff, Rubber Ch.
em. Tech. 55 (1982), 967). It is believed herein that this reaction is the key to the reinforcing action of the organosilane polysulfide coupling agent in the silica reinforced vulcanizable rubber composition or the optionally vulcanized rubber composition.

The third reaction is believed herein to be with a sulfur donor, an organosilane polysulfide as a donor of free sulfur. Due to the thermal stability nature of the S _x (where x is greater than or equal to 3) bridges of the organosilane polysulfide, the energy associated with the thermomechanical mixing of the rubber composition and the associated resulting temperature, especially about 1
It is believed herein that a temperature of 50 ° C. to about 180 ° C. is sufficient to break the sulfur bridges of the organosilane polysulfide having sulfur bridges of 3 or more bound sulfur atoms. Therefore, small amounts of free sulfur are usually formed. Such a small amount of free sulfur is then used for partial vulcanization of the elastomer, much like conventional vulcanization of elastomers. Such partial vulcanization or cure is somewhat a side reaction in the sense that such vulcanization is not considered here as a direct mode of coupling silica to rubber with a silica coupling agent or adhesive. I can think. In fact, such pre- or partial vulcanization or cross-linking of elastomers with free sulfur makes processing significantly more difficult and the resulting rubber composition becomes too viscous to be used in common rubber mixing and / or processing equipment. It may not be processed well, or the viscosity of the resulting rubber composition may differ slightly from batch to batch of rubber, especially as the mixing time or temperature of the rubber composition increases.

Accordingly, and in part, the desired silane-polymer chemistry described above that occurs in the rubber composition mixing step at about 140 ° C. to about 180 ° C. under high shear conditions and three or more bound sulfur atoms. To obtain consistent rubber products from each rubber mixture, as evidenced by rubber products whose physical properties are inconsistent, because of the complex combination of organosilane polysulfides containing bridges with sulfur donor action. Was sometimes difficult. Thus, even if practical, the complexity of the possible reaction mechanisms is such that the organosilane polysulfide reaction and rubber processing can occur during the numerous chemical reactions described above, especially during the non-productive mixing step. It makes it very difficult to properly control the overall reaction of.

[0029]

The formation of the covalent bond between the silane coupling agent on the one hand and the elastomer (the second reaction) and the action of the sulfur donor (the third reaction) on the other hand are at least the organosilane. Not related to each other (decoupled) as far as polysulfides are concerned
In some cases, it was proposed that very different and more controllable sulfur / rubber interactions could be made, and we found this as described below.

In fact, such independence (decoupling) is here considered to be an important and critical aspect of the invention.

To achieve the decoupling action,
Organosilane polysulfides are limited to those that are limited to disulfides or at least relatively pure disulfides. Such high-purity organosilane disulfide is
It contains a minimal, if any, organosilane polysulfide containing sulfur bridges of three or more bound sulfur atoms.

The action of the organosilane disulfide can be explained, for example, as follows: First, the disulfide portion of the organosilane disulfide has a total mixing time of about 1
Less than 5 minutes or possibly 20 minutes or more during the above-mentioned preliminary non-productive rubber mixing step at 140 ° C. to 180 ° C. in a rubber mixer (one or more), especially in a general rubber mixing step or in some cases It does not appreciably or easily form free sulfur during the relatively short individual mixing times of the continuous mixing process. This is because, in the case of organosilane polysulfides, the energy required to break the sulfur-sulfur bond of the disulfide bridge and / or the carbon-sulfur bond adjacent to the disulfide bridge is more than three in the otherwise similar organosilane polysulfide. This is because it is much larger than the energy required to break such a bond of a polysulfide bridge containing a bonded sulfur atom as well.

Therefore, in the method of mixing the vulcanizable rubber, silica and the organosilane polysulfide at high temperature, the reaction relating to the formation of a covalent bond between the organosilane polysulfide and the elastomer (second reaction mentioned above).
Can be decoupled from the sulfur donating action (third reaction above), which adds such an organosilane polysulfide separately and independently, in the form of a polysulfide conversion to a relatively pure disulfide. Vulcanization accelerators, or sulfur sources of free or elemental sulfur, or a combination of vulcanization accelerators and sulfur sources in combination with at least one of the pre-rubber composition mixing steps described above.

Such a sulfur source is, for example, elemental sulfur or S ₈ itself, or in the form of a sulfur donor. Sulfur donors are considered herein as sulfur-containing organic compounds that release free or elemental sulfur at about 140 ° C to about 190 ° C.
Such sulfur donors are, for example, without limitation, polysulfide vulcanization accelerators and organosilane polysulfides having at least three bound sulfur atoms in the polysulfide bridge.

The amount of free sulfur source added to the mixture can be adjusted as a matter of choice relatively unrelated to the addition of the organosilane disulfide. So, for example,
The independent addition of the sulfur source can be adjusted by its addition amount and by the order of addition relative to the addition of other ingredients such as silica reinforcement to the rubber mixture.

As such, organosilane disulfides having two attached sulfur atoms in the sulfur bridge moiety can be used in the first and second related reactions described above, and independent of the sulfur source, especially the free sulfur source. Addition,
It can be mainly used for the above-mentioned third reaction.

Accordingly, it is believed herein that at least partial decoupling of the above reaction has taken place.

Such adjustment of the sulfur / rubber interaction, in combination with the silane / silica interaction described above in the preliminary rubber mixing step, is considered herein to be far from known conventional practice.

It is recognized that the prior patent publications describe the use of organosilane disulfides as silica coupling agents in elastomer formulations. See, for example, U.S. Pat. No. 4,076,550 and German Published Patent Application DT 2,360,470 Al. However, as a means of adjusting the accompanying sulfur / elastomer interaction, the above-described method of the present invention using relatively pure organosilane disulfide in a preliminary rubber-silica mixing step in combination with independent addition of a free sulfur source is , Considered to be inventive, away from conventional practice. It has been found that such a method provides a better reproducibility of the physical properties of the rubber compound as well as a greater degree of flexibility in compounding or mixing as indicated by the adjustable reaction action.

In addition to the above inventive concept, also generally about 1
Addition of alkylsilane to the coupling agent system (organosilane disulfide and additional free sulfur source and / or vulcanization accelerator) at a molar ratio of alkylsilane to organosilane disulfide of / 50 to about 1/2 is used to produce rubber. It is believed herein to promote better control over the composition or formulation, processing, and aging of the formulation that normally occurs under aging conditions such as exposure to moisture and / or ozone.

The term "phr" as used herein means "parts of each material per 100 parts by weight of rubber or elastomer" in accordance with conventional practice.

In describing the present invention, "rubber" and "
If the term "elastomer" is used herein, it may be used interchangeably unless otherwise stated. If the terms "rubber composition" and "rubber compound" are used herein , These refer to rubbers compounded or mixed with various components and materials, and "rubber compounding" or "compounding" may be used to refer to the mixing of such materials. It is well known to those skilled in the rubber compounding art.

The Tg of the elastomer, if used herein, refers to the glass transition temperature which can be measured by a differential scanning calorimeter at a heating rate of 10 ° C./min.

According to one embodiment of the invention, the rubber composition has the following sequential steps: (A) In at least one premixing step, the following ingredients are combined for a total mixing time of about 2 to about 20 minutes, instead of about 4 ~
About 140 to about 190 ° C for about 15 minutes, instead about 150
Thermomechanical mixing at a temperature of from 0 ° C to about 185 ° C: (i) at least one selected from conjugated diene homopolymers and copolymers and copolymers of at least one conjugated diene and aromatic vinyl compound. 100 parts by weight of a vulcanizable elastomer, (ii) a particulate filler comprising at least one of precipitated silica, alumina, aluminosilicates and carbon black from about 15 to about 100 phr, alternatively about 30 phr.
To about 90 phr, wherein the filler contains carbon black of from about 5 to about 85 wt%, (iii) _{^{formula: Z-R 1 -S n -R}} 1 -Z [ wherein, n 2-8 Is an integer of at least 8
0%, preferably about 95 to about 100%, n is 2;
Z is

Embedded image (In the formula, R ² may be the same or different and is individually selected from the group consisting of an alkyl group having 1 to 4 carbon atoms and phenyl; R ³ may be the same or different and has 1 carbon atom; ~ 4 alkyl groups, phenyl, C 1-8 alkoxy groups and C 5-8 cycloalkoxy groups; and R ¹ has a total number of carbon atoms of 1-18. Selected from the group consisting of a substituted or unsubstituted alkylene group and a substituted or unsubstituted arylene group having a total of 6 to 12 carbon atoms)
From about 0.05 to about 20 parts by weight per 1 part by weight of the above-mentioned granular filler; and (iv) (a) (1) elemental sulfur and ( 2) About 14
A free sulfur source selected from at least one of at least one sulfur donor as a sulfur-containing polysulfide-based organic compound having the property of releasing at least a portion of sulfur at 0 ° C to about 190 ° C, provided that The total free sulfur obtained from the addition of elemental sulfur and from the addition of the sulfur donor is from about 0.05 to about 2 phr, or about 0.
2 to about 1 phr, and (b) at least one vulcanization accelerator for a vulcanizable elastomer that is not a sulfur donor as described above from about 0.1 to about 0.5 phr, or about 0.1. At least one additional additive as a compound selected from about 0.3 to about 0.3 phr; and (B) at a final thermomechanical mixing step of about 10
The above ingredients are added at about 0.
Mixing with 4 to about 3 phr elemental sulfur and at least one vulcanization accelerator, provided that the elemental sulfur introduced in the premixing step and the sulfur resulting from the addition of the sulfur donor and the final mixing step The total amount of elemental sulfur added at about 0.45 to about 5 phr.

In one aspect of the invention, such a method comprises premixing in at least two thermomechanical mixing steps, at least two such mixing steps being about 140
C. to about 190.degree. C. and intercool the rubber composition to a temperature of less than about 50.degree. C. during at least two of the mixing steps.

Further in accordance with the present invention, a rubber composition is produced in which the preliminary step (A) comprises at least two successive mixing steps, wherein the elastomer, the particulate filler, and at least 80% n is 2. Alternatively, at least 95% of the organosilane polysulfide compound having an n of 2 is mixed in one or more sequential mixing steps, and the sulfur source and / or vulcanization accelerator is added in a subsequent sequential premixing step.

Still further in accordance with the present invention, a rubber composition is prepared in which the preliminary step (A) comprises at least two sequential mixing steps and comprises from about 20 to about 60 weight percent silica, the organosilane disulfide compound and The sulfur source and / or vulcanization accelerator are added in the first step, and the rest of them are added in at least one subsequent premixing step.

In the method of the present invention, the high-purity organosilane disulfide, that is, at least 80%, or at least 95% of the above organosilane polysulfide compound in which n is 2, is (a) about 25 to about 75% by weight. Preferably about 40 to about 60% by weight of the organosilane polysulfide compound, and correspondingly (b) about 75 to about 25% by weight, preferably about 60 to about 40% by weight.
Optionally added to the thermomechanical premix in the form of granules consisting of granular carbon black. Since high-purity disulfides are generally considered herein to be in liquid, or substantially liquid, form, the purpose of feeding high-purity organosilane disulfide in the form of particulates to the process of the invention is to use carbon in the process of the invention. The addition of relatively pure or substantially dry powdered high purity organosilane disulfide in which the black acts as a carrier for the high purity organosilane disulfide. The advantage of granulating is that it facilitates the dispersion of the high purity organosilane disulfide in the premixing step of the method of the present invention, and aids the introduction of the high purity disulfide into the premix of the rubber composition mixture.

Further in the present invention, the method comprises the additional step of vulcanizing the rubber composition produced at about 140 ° C to about 190 ° C.

Therefore, the present invention also relates to a vulcanized rubber composition produced by such a method.

Further in the present invention, the present method produces an assembly of a tire or vulcanizable rubber and a tread comprising the above rubber composition produced by the method of the present invention,
An additional step of vulcanizing this assembly at about 140 ° C to about 190 ° C is included.

Therefore, the present invention also relates to a vulcanized tire produced by such a method.

In one embodiment of the present invention, optionally a total of about 0.05 to about 5 phr of at least one alkylsilane, especially an alkylsilane of the formula R'-Si- (OR) ₃ , is used in the premixing step described above. Thermomechanical mixing is possible, where R is a methyl, ethyl, propyl or isopropyl group and R'is a saturated alkyl group having 1 to 18 carbon atoms or an aryl or saturated alkyl group having 6 to 12 carbon atoms. It is an aryl group. Such aryl or substituted aryl groups are, for example, benzyl, phenyl, tolyl, methyltolyl and alphamethyltolyl groups.

The purpose of the alkylsilanes is, for example, to improve the incorporation of fillers and the aging of the formulation. Representative examples of alkylsilanes include, but are not limited to, for example, propyltriethoxysilane, methyltriethoxysilane, hexadecyltriethoxysilane and octadecyltriethoxysilane.

A feature of the present invention is the addition of relatively high purity organosilane disulfide to a sulfur source such as elemental sulfur and / or a sulfur donor, and / or vulcanization acceleration not considered here as a sulfur donor. Used in combination with the addition of an agent, by thermomechanically mixing the materials in at least one premixing stage to about 140 ° C to about 180 ° C.
The silica coupling agent / granular filler composition is prepared in situ in the rubber composition in a preliminary step. In fact, by using this method, the rubber mixing process is about 140 ° C.
It may be envisaged to perform at higher temperatures, such as up to about 190 ° C.

This is, for example, 3,3'-bis (trialkoxyalkylsilyl) tetrasulfide or trisulfide in the absence of other sulfur sources from about 140 ° C to about 180 ° C.
It is believed to be well off the practice used in the non-productive rubber composition mixing stage at 0 ° C.

In the practice of the present invention, the amount of sulfur introduced into the premix or released from the sulfur donor is generally from about 0.05 to about 2, or from about 0.2 to about 1. . The addition of sulfur is recognized as meaning the decoupling of the silane reaction of the organosilane polysulfide with the reaction of free sulfur released from the polysulfide moiety. This is achieved in the present invention by using a relatively high purity disulfide which does not appreciably release sulfur under the above conditions, so that sulfur can be added, for example as free sulfur or separately from a sulfur donor. it can. In this sense, the amount of free sulfur that can be added to the premix during the practice of the present invention will generally result from the organosilane polysulfide, if the sulfur bridge contains about 3-8 sulfur atoms. It is almost equal to the expected free sulfur. The actual calculation is somewhat difficult because of the need to determine the actual number of sulfur atoms in the sulfur bridge, but the range of sulfur added is more easily indicated here by phr, ie per 100 parts of rubber. This is at least 80
%, Or at least 95% of n is 2 and the remaining n is an integer from 3 to about 8, ie, at least 80
%, Or at least 95% of the organosilane polysulfide is an organosilane disulfide, is believed to provide a suitable amount of added free sulfur to the organosilane polysulfide. As mentioned above, in the premixing of the method of the present invention, vulcanization accelerators not considered here as sulfur donors can also be added as an alternative to the sulfur source. Those of ordinary skill in the rubber mixing art will readily be able to optimize the addition of the sulfur source to the premix depending on the mixing and processing conditions desired and the properties of the resulting rubber composition.

In the practice of the present invention, the sulfur donor for the preliminary step is a polysulfide vulcanization accelerator for vulcanizable elastomers and an organosilane polysulfide having a polysulfide moiety containing at least three bound sulfur atoms. It is selected from at least one.

The additional vulcanization accelerators which may be mentioned here are:
For example, those of the kind such as benzothiazole, alkyl thiuram disulfide, guanidine derivatives and thiocarbamates. Representative examples of such accelerators are, for example, mercaptobenzothiazole, tetramethylthiuram disulfide, benzothiazole disulfide, diphenylguanidine, zinc dithiocarbamate, alkylphenol disulfide, zinc butylxanthate,
N-dicyclohexyl-2-benzothiazole sulfenamide, N-cyclohexyl-2-benzothiazole sulfenamide, N-oxydiethylenebenzothiazole-2-sulfenamide, N, N-diphenylthiourea, dithiocarbamylsulfene Amides, N, N-diisopropylbenzothiazole-2-sulfenamide, zinc-2-mercaptotoluimidazole, dithiobis (N-methylpiperazine), dithiobis (N-betahydroxyethylpiperazine) and dithiobis (dibenzylamine). However, it is not limited to these. It is believed that such materials are well known to those skilled in the rubber compounding art as vulcanization accelerators for vulcanizable elastomers.

Additional sulfur donors of the type such as thiuram and morpholine derivatives are recognized. Representative examples of such donors are, for example, dimorpholine disulfide, dimorpholine tetrasulfide, tetramethylthiuram tetrasulfide, benzothiazyl-2, N dithiomorpholide, thioplasts, dipentamethylene thiura hexasulfide and disulfide caprolactam, Not limited to. Such materials are considered to be sulfur donors well known to those skilled in the rubber compounding art.

For the additional sulfur donors described above, organosilane polysulfides having three or more bound sulfur atoms in the polysulfide bridge can be used. Typical examples thereof include, for example, 3,3'-bis (trimethoxysilylpropyl) trisulfide and tetrasulfide, 3,3 '.
-Bis (triethoxysilylpropyl) trisulfide and tetrasulfide, 3,3'-bis (triethoxysilylethyltrilene) trisulfide and tetrasulfide, and Huels AG polysulfide organosilane T47, but is not limited thereto. .

If a rubber composition containing silica-based fillers, such as silica, alumina and / or aluminosilicates, which are mainly reinforced with silica as reinforcing pigment, and also carbon black reinforcing pigments, is preferred. The weight ratio of earth pigment silicate to carbon black is at least 3/1, preferably at least 10/1, and thus from about 3/1 to about 30/1.

In one aspect of the invention, the siliceous pigment is preferably precipitated silica.

In another aspect of the invention, the filler is between about 15 and.
About 95% by weight precipitated silica, alumina and / or aluminosilicate, and correspondingly about 5 to about 85% by weight.
The carbon black has a CTAB value of about 80 to about 150.

In practicing the present invention, the filler is about 60-.
About 95% by weight of the above silica, alumina and / or aluminosilicate, and correspondingly about 40 to about 5% by weight.
Made of carbon black.

For the above organosilane disulfide compounds, a typical R ² group is an alkyl group and a typical R ¹ group is selected from alkaryl, phenyl and haloaryl groups.

Thus, in one aspect of the invention, the R ² and R ¹ groups are mutually exclusive.

Typical examples of the alkyl group are methyl, ethyl and n.
-Propyl and n-decyl groups.

Representative examples of aralkyl groups are benzyl and alpha, alpha-dimethylbenzyl groups.

Representative examples of alkaryl groups are p-tolyl and p-nonylphenol groups.

A typical example of the haloaryl group is p-chlorophenol group.

Representative examples of the organosilane disulfide of the above organosilane polysulfide compound are, for example, the following compounds: 2,2'-bis (trimethoxysilylethyl) disulfide; 3,3'-bis (trimethoxysilylpropyl) Disulfide; 3,3'-bis (triethoxysilylpropyl) disulfide; 2,2'-bis (triethoxysilylpropyl) disulfide; 2,
2'-bis (tripropoxysilylethyl) disulfide; 2,2'-bis (tri-sec-butoxysilylethyl) disulfide; 3,3'-bis (tri-t-butoxyethyl) disulfide; 3,3'-bis (Triethoxysilylethyltolylene) disulfide; 3,3'-bis (trimethoxysilylethyltolylene) disulfide; 3,3'-bis (triisopropoxypropyl) disulfide; 3,3'-bis (trioctoxy Propyl) disulfide; 2,2'-bis (2'-ethylhexoxysilylethyl) disulfide; 2,2'-bis (dimethoxyethoxysilylethyl) disulfide;
3,3'-bis (methoxyethoxypropoxysilylpropyl) disulfide; 3,3'-bis (methoxydimethylsilylpropyl) disulfide; 3,3'-bis (cyclohexoxydimethylsilylpropyl) disulfide; 4,4'-bis (Trimethoxysilylbutyl) disulfide; 3,3'-bis (trimethoxysilyl-3
-Methylpropyl) disulfide; 3,3'-bis (tripropoxysilyl-3-methylpropyl) disulfide; 3,3'-bis (dimethoxymethylsilyl-3-ethylpropyl) disulfide; 3,3'-bis (tri Methoxymethylsilyl-2-methylpropyl) disulfide; 3,3'-bis (dimethoxyphenylsilyl-2-
Methylpropyl) disulfide; 3,3'-bis (trimethoxysilylcyclohexyl) disulfide; 12,
12'-bis (trimethoxysilyldodecyl) disulfide; 12,12'-bis (triethoxysilyldodecyl) disulfide; 18,18'-bis (trimethoxysilyloctadecyl) disulfide; 18,18'-bis (methoxydimethylsilyl) Octadecyl) disulfide; 2,2'-bis (trimethoxysilyl-2-methylethyl) disulfide; 2,2'-bis (triethoxysilyl-2-methylethyl) disulfide; 2,2'-
Bis (tripropoxysilyl-2-methylethyl) disulfide; and 2,2'-bis (trioctoxysilyl-2-methylethyl) disulfide.

In practicing the present invention, as pointed out above,
The rubber composition comprises at least one diene-based elastomer or rubber. Suitable conjugated dienes are isoprene and 1,3-butadiene, and suitable vinyl aromatic compounds are styrene and alphamethylstyrene. Therefore, the elastomer is considered to be a vulcanizable elastomer. Such diene-based elastomers or rubbers are, for example, cis 1,4-polyisoprene rubbers (natural and / or synthetic rubbers, preferably natural rubbers), emulsion-produced styrene / butadiene copolymer rubbers, organic solutions. Styrene / butadiene rubber produced by polymerization, 3,4-polyisoprene rubber, isoprene / butadiene rubber, styrene / isoprene / butadiene terpolymer rubber, cis 1,4-polybutadiene, vinyl polybutadiene with medium vinyl content Rubber (35-50% vinyl), polybutadiene rubber with high vinyl content (50-75% vinyl), styrene / isoprene copolymer, styrene / butadiene / acrylonitrile terpolymer rubber and butadiene / produced by emulsion polymerization Acrylonitrile copolymerization It may be selected from at least one rubber.

In one embodiment of the present invention, emulsion polymerization-derived styrene / butadiene (E-SB) has a relatively common styrene content of about 20 to about 28% bound styrene.
R), or in some cases, E-SBR having a relatively high bound styrene content, ie, a bound styrene content of about 30 to about 45% may be used.

A relatively high styrene content of E-SBR of about 30 to about 45% may be considered advantageous for increasing the traction or skid resistance of the tire tread. In particular, the presence of E-SBR itself is considered to be advantageous for enhancing the processability of the unvulcanized elastomer composition mixture, as compared with the case of using SBR produced by solution polymerization (S-SBR). .

E-SBR produced by emulsion polymerization
Means that styrene and 1,3-butadiene are copolymerized as an aqueous emulsion. Such is well known to those skilled in the art. The bound styrene content can vary, for example from about 5 to 50%. In one aspect, the E-SBR may also contain, for example, from about 2 to about 30 weight percent bound acrylonitrile in the terpolymer to form a terpolymer rubber such as E-SBR.

Emulsion polymerized styrene / butadiene / acrylonitrile terpolymer rubbers containing from about 2 to about 40 weight percent bound acrylonitrile are also contemplated as diene-based rubbers for use in the present invention.

SBR produced by solution polymerization (S-SB
The bound styrene content of R) is generally from about 5 to about 50%,
It is preferably about 9 to about 36%. S-SBR can be conveniently prepared, for example, by organolithium catalysis in the presence of organic hydrocarbon solvents.

The purpose of using S-SBR is to improve tire rolling resistance as a result of reduced hysteresis when used in tire tread compositions.

3,4-polyisoprene rubber (3.4-P
I) is believed to be advantageous for increasing tire traction when it is used in a tire tread composition.

For 3,4-polyisoprene elastomers and their use, see US Pat. No. 5,087,668.
In more detail, which is hereby incorporated by reference.

The cis 1,4-polybutadiene rubber is considered to be advantageous for enhancing the wear resistance of the tire tread, that is, the tread wear resistance.

Such polybutadiene elastomers can be produced, for example, by organic solution polymerization of 1,3-butadiene as is well known to those skilled in the art.

The polybutadiene elastomer is conveniently characterized, for example, by a cis 1,4-content of at least 90%.

Cis 1,4-polyisoprene and cis 1,4-polyisoprene natural rubber are well known to those having skill in the rubber art.

The vulcanized rubber composition should contain sufficient amounts of silica, carbon black (if used), and reinforcing filler to be of reasonably high modulus and high tear resistance. The total weight of silica, alumina, aluminosilicate and carbon black may be as low as about 30 parts per 100 parts of rubber, as described above, but is more preferably about 35 to about 90 parts by weight.

It is contemplated herein that common siliceous pigments used in rubber compounding can be used as silica in the present invention, including, for example, pyrolytic and precipitated siliceous pigments (silica). Alumina, aluminosilicate and precipitated silica are preferred.

The siliceous pigments preferred for use in the present invention are those obtained by acidification of precipitated silica, for example soluble silicates such as sodium silicate. Such precipitated silicates are well known to those skilled in the art.

Such precipitated silicas, for example, have a BET surface area, measured using nitrogen gas, preferably in the range of about 40-.
About 600 m ² / g, more usually about 50 to about 300 m ² / g
It has the characteristic of being For the BET method for measuring the surface area, see Journalof the American
an Chemical Society , Volume 60,
P. 304 (1930).

Silica is dibutyl phthalate (DBP)
It is generally characterized by an absorption value of about 100 to about 350, more usually about 150 to about 300.

In addition, the CTAB surface area of silica, and the above aluminas and aluminosilicates, is required to be from about 100 to about 220. CTAB surface area is p
External surface area as measured by cetyltrimethylammonium bromide at H9. About the method
The setting and evaluation method is described in D 3849.
CTAB surface area is a well-known means for characterizing silica.

Mercury surface area / porosity is the specific surface area measured by mercury porosimetry. In such a method, mercury is permeated into the pores of the sample after heat treatment to remove volatile substances. The setting condition is to use a 100 mg sample; remove volatile substances at 105 ° C. and ambient atmospheric pressure for 2 hours; and measure at ambient pressure to 2000 bar pressure. Such an assessment is Winslow,
It may be carried out according to the method described in Shapiro, ASTM bulletin, page 39 (1959) or DIN 66133. In order to make such an evaluation, CAR
LO-ERBA Porosimeter 2000 may be used.

The average mercury porosity specific surface area of silica is about 10
It should be 0-300 m ² / g.

Silica by such mercury porosity evaluation,
Suitable pore size distributions for alumina and aluminosilicates are considered here to be: 5
% Or less pore diameter is less than about 10 nm; 60-9
0% pore diameter is about 10 to about 100 nm; 10
-30% pore diameters are about 100 to about 1000 nm; and 5-20% pore diameters are greater than about 1000 nm.

The average ultimate particle size of silica measured with an electron microscope is required to be, for example, 0.01 to 0.05 micron, but even if the silica particles are smaller than this,
May be large.

Various commercially available silicas can be used in the present invention, examples of which are H-Sil 201, 243 and the like.
Silica sold by PPG Industries, Inc. under the trade name i-Sil; eg Zeosil 1165M.
Silica sold by Rhone-Poulenc under the P trade name, eg D under the trade names VN2, VN3, etc.
Silicas sold by the company Egussa and, for example, silicas sold by the company Huber under the trade name Hubersil 8745, but not limited thereto.

Typical of the aluminas which can be used for the purposes of the present invention are natural and synthetic alumina oxides (Al ₂ O ₃ ).
Such alumina can be successfully synthesized, for example, by controlled precipitation of aluminum hydroxide. For example,
Natural acidic and basic Al ₂ O ₃ are available from Aldrich Chemical Company. In the practice of the present invention,
Neutral alumina is preferred, but it is contemplated herein that acidic, basic and neutral forms of alumina may be used. In order to reduce the interference with the desired reaction of the alumina with the organosilane disulfide coupling agent, the neutral or substantially neutral form should have a reduced number of surface -OH groups compared to the acidic form. It is shown as being preferred for use and also for reducing the basic sites of the alumina, which are AlO − ions which represent strong bases.

Representative examples of aluminosilicates which can be used for the purposes of the present invention are, for example, Tolsa, Toledo, Spain.
, But not limited to, the natural aluminosilicate sepiolite available as PANSIL from the company and the synthetic aluminosilicate SILTEG available from Degussa. Such aluminosilicates can be used as natural or synthetic materials as exemplified above.

The rubber composition is prepared by a method generally known in the rubber compounding field, for example, various vulcanizable constituent rubbers and various commonly used additive materials such as sulfur, activators, retarders and accelerators. Auxiliaries, processing additives such as oil,
Mix with resins including tackifiers, silica, and plasticizers, fillers, pigments, fatty acids, zinc oxide, waxes, antioxidants and antiozonants, peptizers, and reinforcing agents such as carbon black. It is easily understood by a person skilled in the art to formulate by mixing. As will be apparent to those skilled in the art, depending on the vulcanizability and the intended use of the vulcanized material (rubber), the above additives will generally be selected and used in conventional amounts.

If used, the reinforced tie of the present invention.
The general amount of carbon black used is
is there. Silica coupling agent with carbon black
It may be used, i.e., it may be added to the rubber composition prior to addition to the rubber composition.
May be premixed with Bon Black, and such a
Carbon black is the above-mentioned carbon for rubber composition.
It is contained in the amount of bon black. Sticky if used
The general amount of the imparting resin used is about 0.5 to about 10 ph.
r, usually about 1 to about 5 phr. Common processing aids
The amount is from about 1 to about 50 phr. Such processing aids
Is, for example, aromatic naphthenic and / or paraffinic
Process oil. Typical amounts of antioxidants range from about 1 to about
5 phr. Typical oxidants are, for example, diphenyl
-P-phenylenediamine, and others such asV
anderbilt RubberHandbook
(1978) pp. 344-346
Is. Typical amounts of antiozonants are from about 1 to about 5 p.
It is hr. Fats, including stearic acid, if used
Typical amounts of fatty acids are about 0.5 to about 3 phr. Oxidation
Typical amounts of zinc are about 2 to about 5 phr. wax
Typical amounts are from about 1 to about 5 phr. Often my
Clocrystallin wax is used. Peptizer
Typical amounts are about 0.1 to about 1 phr. General
Pyrolytic agents include, for example, pentachlorothiophenol and dichloromethane.
It is benzamide diphenyl disulfide.

Vulcanization is carried out in the presence of a vulcanizing agent. Examples of suitable vulcanizing agents are elemental sulfur (free sulfur) or sulfur donating vulcanizing agents such as amine disulfides, high molecular weight polysulfides or sulfur olefin adducts, which are commonly used in the final productive rubber composition mixing step. Added. In most cases, it is preferred that the vulcanizing agent be elemental sulfur. As will be apparent to those skilled in the art, the vulcanizing agent is from about 0.4 to about 3 ph.
r, optionally used in the productive mixing stage in an amount of about 8 phr or less, i.e., about 1.5 to about 2.5.
It is usually preferred to have a phr, sometimes 2-2.5 phr.

Accelerators are used to adjust the time and / or temperature required for vulcanization and to improve the properties of vulcanized rubber. In one embodiment, a single accelerator system, namely the first
Accelerators may be used. The total amount of first accelerator is about 0.5 to about 4 phr, preferably about 0.8 to about 1.5 phr. In another embodiment, a combination of a first accelerator and a second accelerator is used, with the second accelerator being in a smaller amount (about 0.05-about) to activate and improve the properties of the vulcanized rubber.
Used at about 3 phr). The combination of these accelerators is expected to have a synergistic effect on the final properties,
Somewhat better than those made with either accelerator alone. In addition, slow-acting accelerators which are not affected by normal processing temperatures but which cure well at normal vulcanization temperatures may be used. Vulcanization retarders may be used. Suitable types of accelerators that can be used in the present invention are amines, disulfides, guanidines, thioureas, thiazoles, thiurams, sulfenamides, dithiocarbamates and xanthates. The first accelerator is preferably sulfenamide. If a second accelerator is used, it is preferably a guanidine, dithiocarbamate or thiuram compound.

The rubber composition of the present invention can be used for various purposes. For example, it can be used in various tire formulations. Such tires can be manufactured, molded and cured by various methods known and apparent to those skilled in the art.

The present invention will be described in more detail by the following examples. Parts and percentages in the examples are by weight unless otherwise stated.

[0105]

EXAMPLE I A vulcanizable rubber mixture containing silica reinforcement was added to 3,3-
It was prepared using bis (triethoxysilylpropyl) tetrasulfide and high-purity 3,3-bis (triethoxysilylpropyl) disulfide, respectively.

The above organosilane tetrasulfide sulfur bridge moieties contain an average of about 3.5 to about 4 bound sulfur atoms, the range of bound sulfur atoms is about 2 to 6 or 8 and up to 25% of that sulfur. It is considered that the bridge portion has 2 or less bound sulfur atoms.

The above-mentioned organosilane polysulfide and high-purity organosilane disulfide were sequentially and stepwise mixed with the elastomer and compounding components in a series of premixing steps.

When using high purity 3,3-bis (triethoxysilylpropyl) disulfide, a small amount of free sulfur is also added to the first premix stage. In the final mixing stage, additional and above quantitative amounts of free sulfur are added along with accelerators.

After each mixing step, the rubber mixture was dispensed on a roll machine, kneaded and mixed for a short time, the rubber removed from the roll machine was slabed and cooled to below about 30 ° C.

Rubber compositions containing the materials shown in Table 1 were prepared as follows:
Three separate additions (mixing) at temperatures of 160 ° C, 160 ° C and 120 ° C, respectively, times of about 8 minutes, 2 minutes and 2 minutes
Made in a BR Banbury mixer using two stages, namely two premix stages and one final mix stage. The amounts of organosilane tetrasulfide, organosilane disulfide and free elemental sulfur are noted in Table 1 as "variable" and in more detail in Table 2.

Comparing Samples 2 and 3 using high-purity organosilane disulfide with Sample 1 using organosilane polysulfide, high-purity organosilane disulfide was used as a means for adjusting the mixing process of the silica-reinforced elastomer. The advantages of using it in combination with addition are well understood.

[0112]

[Table 1]

1) Combination of elastomers, ie cis at a dry rubber weight ratio of 10/25/45/20.
1,4-polyisoprene natural rubber, E-SBR containing about 40% styrene with Tg of about -31 ° C (Goodyear Tire & Rubber Co.), isoprene with Tg of about -44 ° C /
Butadiene (50/50) copolymer elastomer (Goodyear Tire & Rubber), and BUD 1
Cis 1,4-polybutadiene elastomer obtained as 207 (Goodyear Tire & Rubber Co.);
The E-SBR is oil extended to contain 25 phr gum and 15 phr oil. 2) Phenylenediamine type; 3) Zeosil of Rhone Poulenc
1165 MP; 4) Si69 [previously referred to herein as bis- (3-triethoxysilylpropyl) tetrasulfide (this tetrasulfide is also available from Degussa as Si69)] and carbon black. Deguss as X50S in the form of a 50/50 blend of
The composite material available from Company a, ie tetrasulphide, is 50% of the composite material and therefore 50% of the activator.
And 5) Obtained as S ₈ elemental sulfur from Kali Chemie GmbH of Germany.

The high-purity organosilane disulfide is obtained by adding, for example, 500 parts by weight of mercaptopropyltriethoxysilane to about 320 parts by weight of magnesium dioxide,
It can be successfully prepared by oxidizing mercaptopropyltriethoxysilane over magnesium dioxide under conditions where the mixture is shaken vigorously. The reaction initially occurs at about room temperature, or about 23 ° C, and then rises to about 90 ° C due to the exothermic reaction process. Then about 50
Add 0 parts by weight of dry toluene. The reaction of the mixture is about 5
Continue at 0 ° C for about 1 hour. The magnesium dioxide is then removed by filtration and the remaining organic phase is filtered.

The purity of the organosilane disulfide was determined to be at least 98% by weight. That is,
The value of at least 98% of n when the organosilane polysulfide compound was used in the method of this example was 2. Purity is NMR (nuclear magnetic resonance), and i) GC-M
S, gas chromatography mass spectrometry, and ii) HPLC, high performance liquid chromatography.

[0116]

[Table 2]

1) Sulfur was added in a preliminary non-productive mix stage; 2, 3, 4) Non-productive mix stage 1 and stage 2 respectively
(NP1 and NP2) and Mooney viscosity (ML-4) of the rubber mixture from the productive mixing stage (P); and 5) Mooney of the rubber mixture from the NP1 mixing stage (M) (M
L-4) Peak value means the maximum Mooney value determined from the Mooney curve plotted as Mooney vs. time.

In particular, from this example, the high purity organosilane disulfide and a very small amount of free sulfur, that is, the estimated free sulfur generated in the mixing step when using organosilane tetrasulfide (Example 3), are close to each other. It can be seen that by adjusting the addition of the amount of free sulfur, a rubber composition having properties somewhat similar to those of the rubber composition of Example 1 using organosilane tetrasulfide can be obtained.

From this example, further, the adjustment of the amount of free sulfur in the non-productive rubber mixing stage, as particularly demonstrated by Example 1 vs. Example 3, is a processing adjustment of rubber compounds with equal properties. It turns out that it is advantageous to. In one aspect, the DIN abradability of Example 2 is significantly lower than that of Examples 1 and 3. This is believed to be an advantage when using organosilane disulfides without modified sulfur additions, as such properties are sometimes considered to exhibit tire tread wear resistance. Nevertheless, the use of free sulfur in the rubber mixture of Example 3 is still advantageous as tire rolling resistance appears to be improved as evidenced by thermoelastic rebound and tan delta values. Think

In addition, the Mooney plasticity value as a measure of the viscosity of the rubber mixture was determined by processing the formulation as evidenced by the Mooney values shown in Table 2, especially the Mooney peak value of the rubber from the unproductive mixing stage. As far as is concerned, it emphasizes the advantage of using disulfides without the addition of free sulfur as compared to the use of organosilane tetrasulfides, these values being from Example 2 to Example 3 and to Example 1. It is getting bigger and bigger.

Therefore, when the vulcanizable elastomer, silica and the organosilane polysulfide coupling agent are mixed at high temperature, (i) formation of a covalent bond between the organosilane polysulfide and the elastomer (the above second reaction) is ii) It is now considered that it has been proved that a method for decoupling from the sulfur donating action (the third reaction above) has been provided.

Example II Size 195 / 65R15 tires were produced using the rubber compositions of Examples 1, 2 and 3 for their treads. The results shown in Table 3 were obtained:

[Table 3]

1) Indicates a high speed value. For example, in the case of Example 3, using a value of 8'15 "/ 270, this would be 8 minutes 15 seconds for the tire at a corresponding car speed of 270 km / h (not the speed of rotation) on a suitable dynamometer. It means having endured.

This example shows that the tire with the tread of the rubber composition of Example 3 provides tire rolling resistance and tread wear resistance similar to the tire with the tread of the rubber composition of Example 1. ing.

When the tread of Example 3 is used for the tire,
Compared to Example 1, the processing of the improved non-vulcanized formulation is believed to be advantageous here because it provides the best balance of properties, namely wet skid, tread wear resistance and rolling resistance. Example 2 showed higher tread wear resistance and better wet skid on asphalt.

While specific representative examples and details have been set forth for the purpose of describing the invention, it will be apparent to those skilled in the art that changes may be made without departing from the spirit or scope of the invention.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display area C08K 3/34 C08K 3/34 3/36 KCX 3/36 KCX 5/36 KDN 5/36 KDN 5 / 54 KDV 5/54 KDV // B29K 21:00 B29L 30:00 (71) Applicant 590002976 1144 East Market Street, Akron, Ohio 44316-0001, U.S.A. S. A. (72) The inventor Thiel Florent Edom Matterne, Belgium-6717, Athel, Rue de la Liberation 10 (72) The inventor, Giorgio Agostini, The Grand Duchy of Luxembourg, El-7733 Colmar-Berg, Liu・ De Luxe Burger 7 (72) Inventor Friedrich Wizel, Grand Duchy of Luxembourg El-7378 Boferdange, Rue Nopener 9a (72) Inventor Uwe Ernst Frank, Grand Duchy of Luxembourg El-9080 Ether Brook, Av New Salentini 103

Claims (76)

[Claims] 1. The following sequential steps: (A) In at least one premix step, the following ingredients are combined for a total mixing time of about 2 to about 20 minutes, about 140 to about 1.
Thermomechanical mixing at 90 ° C .: (i) at least one vulcanizate selected from conjugated diene homopolymers and copolymers and copolymers of at least one conjugated diene and aromatic vinyl compounds. 100 parts by weight of elastomer, (ii) about 15 to about 100 phr of granular filler containing at least one of precipitated silica, alumina, aluminosilicates and carbon black, wherein the filler is about 5 to about 85 wt% carbon. containing black, (iii) formula: _{^{Z-R 1 -S n -R 1}} -Z [ wherein, n is an integer of 2-8, provided that at least 8
0% n is 2; Z is (In the formula, R ² may be the same or different and is individually selected from the group consisting of an alkyl group having 1 to 4 carbon atoms and phenyl; R ³ may be the same or different and has 1 carbon atom; ~ 4 alkyl groups, phenyl, C 1-8 alkoxy groups and C 5-8 cycloalkoxy groups; and R ¹ has a total number of carbon atoms of 1-18. Selected from the group consisting of a substituted or unsubstituted alkylene group and a substituted or unsubstituted arylene group having a total of 6 to 12 carbon atoms)
From about 0.05 to about 20 parts by weight per 1 part by weight of the above-mentioned granular filler; and (iv) (a) (1) elemental sulfur and ( 2) About 14
At least one of at least one sulfur donor as a sulfur-containing polysulfide-based organic compound having a property of releasing at least a part of sulfur at 0 ° C to about 190 ° C.
A source of free sulfur selected from the species, provided that the total of the free sulfur obtained from the addition of the elemental sulfur and from the addition of the sulfur donor is from about 0.05 to about 2 phr, and (b) as described above. At least one vulcanization accelerator for sulfur vulcanizable elastomers that are not unique sulfur donors.
At least one additional additive as a compound selected from 1 to about 0.5 phr; and (B) thereafter in a final thermomechanical mixing step, the above ingredients are added at about 100 to about 130 ° C. for about 1 to about 3 minutes. , About 0.4
To about 3 phr elemental sulfur and at least one sulfur vulcanization accelerator, provided that elemental sulfur and / or free sulfur introduced in the premixing step and elemental sulfur added in the final mixing step. Is about 0.45
A method of making a rubber composition comprising about 5 phr. 2. A total of about 0.05 to about 5 phr of at least one alkylsilane is added to the prethermo-mechanical mixing step, the alkylsilane having the formula: R'-Si- (OR) _3.
Wherein R is a methyl, ethyl, propyl or isopropyl group and R ′ is a saturated alkyl group having 1 to 18 carbon atoms or an aryl or saturated alkyl substituted aryl group having 6 to 12 carbon atoms. The method of claim 1. 3. The method of claim 2, wherein the alkylsilane is selected from one or more of propyltriethoxysilane, methyltriethoxysilane, hexadecyltriethoxysilane and octadecyltriethoxysilane. 4. The rubber composition wherein the premixing is carried out in at least two thermomechanical mixing steps, at least two of such mixing steps are between about 140 ° C. and about 190 ° C. and the rubber composition is between at least two of the mixing steps. The method of claim 1, wherein the intercooling of is less than about 50 ° C. 5. The method of claim 1 including the additional step of vulcanizing the rubber composition produced at about 140 ° C to about 190 ° C. 6. A vulcanized rubber composition produced by the method of claim 5. 7. An additional step of producing an assembly of a sulfur vulcanizable rubber tire and a tread comprising the rubber composition and vulcanizing the assembly at about 140 ° C. to about 190 ° C.
The method of claim 1. 8. A vulcanized rubber tire produced by the method of claim 7. 9. The method of claim 4 including the additional step of vulcanizing the rubber composition produced at about 140 ° C to about 190 ° C. 10. A vulcanized rubber composition produced by the method of claim 9. 11. The method of claim 4 including the additional step of producing an assembly of a vulcanizable rubber tire and a tread comprising the rubber composition and vulcanizing the assembly at about 140 ° C. to about 190 ° C. the method of. 12. Manufactured by the method of claim 11,
Vulcanized rubber tire. 13. The method of claim 1, wherein for the vulcanizable elastomer, the conjugated diene is selected from isoprene and 1,3-butadiene and the vinyl aromatic compound is selected from styrene and alphamethylstyrene. 14. The vulcanizable elastomer is a natural or synthetic cis 1,4-polyisoprene rubber, a styrene / butadiene copolymer rubber produced by emulsion polymerization,
Styrene / butadiene copolymer rubber produced by organic solution polymerization, 3,4-polyisoprene rubber, isoprene / butadiene rubber, styrene / isoprene / butadiene terpolymer rubber, cis 1,4-polybutadiene rubber, vinyl content Is a medium vinyl polybutadiene rubber (35-35
50% vinyl), polybutadiene rubber having a high vinyl content (50 to 75% vinyl), at least one selected from styrene / butadiene / acrylonitrile terpolymer rubber and butadiene / acrylonitrile copolymer rubber produced by emulsion polymerization. The method of claim 1, wherein: 15. The silica has a BET surface area of about 100-.
About 300 m ² / g, dibutyl phthalate (DBP) absorption value about 150 to about 350, CTAB value about 100 to about 2.
20 and the pore size distribution by mercury porosimetry: less than 5%, the diameter of the pores is less than about 10 nm; 6
0 to 90% of the pore diameters are about 10 to about 100 nm; 10 to 30% of the pore diameters are about 100 to about 1000.
nm; and 5-20% pore diameter is about 100 nm.
The method of claim 1, characterized in that it is greater than 0 nm. 16. The filler comprises from about 15 to about 95% by weight precipitated silica, and correspondingly from about 5 to about 85% by weight carbon black;
16. The method of claim 15, having a CTAB value of about 150. 17. The method of claim 16, wherein the filler comprises about 60 to about 95 wt% silica, and correspondingly about 40 to about 5 wt% carbon black. 18. The filler is about 15 to about 100% by weight.
Alumina, and correspondingly about 5 to about 85% by weight of carbon black;
It has a CTAB value of about 150 and the alumina is about 100.
Pore size distribution by mercury porosimetry having a CTAB value of from about 220 to about 220: less than about 5% of pores has a diameter of less than about 10 nm;
The method of claim 1, wherein 0 to about 100 nm; 10 to 30% of the pores have a diameter of about 100 to about 1000 nm; and 5 to 20% of the pores have a diameter of greater than about 1000 nm. 19. The method of claim 18, wherein the filler comprises about 60 to about 95 wt% alumina, and correspondingly about 40 to about 5 wt% carbon black. 20. The filler is about 15 to about 100% by weight.
Aluminosilicates, and correspondingly from about 5 to about 85% by weight of carbon black; said carbon black having a CTAB value of from about 80 to about 150 and said aluminosilicate having a CTAB value of from about 100 to about 220. Have,
And the pore size distribution by mercury porosimetry is: 5%
The diameter of the pores of less than about 10 nm; 60-90
% Pore diameter is about 10 to about 100 nm; 10 to
The method of claim 1, wherein 30% of the pore diameters are about 100 to about 1000 nm; and 5 to 20% of the pore diameters are greater than about 1000 nm. 21. The method of claim 20, wherein the filler comprises about 60 to about 95 wt% aluminosilicate, and correspondingly about 40 to about 5 wt% carbon black. 22. The pH of a (a) a natural aluminosilicate selected from muscovite, beryl, dichroite, sepiolite and kaolinite and (b) a basic solution or mixture of (i) silicate and aluminate. By coprecipitation by conditioning or (ii) silanol and NaAlO _{2 on} the surface of silicon dioxide
The method of claim 1 selected from at least one synthetic aluminosilicate produced by a chemical reaction with. 23. The method of claim 22, wherein for the synthetic co-precipitated aluminosilicate, about 5 to about 95% of its surface comprises silica moieties and correspondingly about 95 to about 5% of its surface comprises aluminum moieties. . 24. The synthetic aluminosilicate has the formula:
[(Al ₂ O ₃ ) _x · (SiO ₂ ) _y · (H ₂ O) _z ];
_{[(Al 2 O 3) x} · (SiO 2) y · MO] ( wherein, M is a is magnesium or calcium) represented by the method of claim 20. 25. The sulfur donor additional additive is selected from at least one of dimorpholine tetrasulfide, tetramethylthiuram tetrasulfide, benzothiazyl-2, N-dithiomorpholide, thioplasts, dipentamethylene thiuram hexasulfide and disulfide caprolactam. The method of claim 1, wherein the method is selected. 26. The vulcanization accelerator for a sulfur vulcanizable elastomer additional additive is mercaptobenzothiazole, tetramethylthiuram disulfide, benzothiazole disulfide, diphenylguanidine, zinc dithiocarbamate, alkylphenol disulfide, zinc butylxanthogenate. , N-dicyclohexyl-2-benzothiazole sulfenamide, N-cyclohexyl-2-benzothiazole sulfenamide, N-oxydiethylene benzothiazole-2-sulfenamide,
N, N-diphenylthiourea, dithiocarbamylsulfenamide, N, N-diisopropylbenzothiazole-2-sulfenamide, zinc-2-mercaptotoluimidazole, dithiobis (N-methylpiperazine), dithiobis (N-beta The method of claim 1 selected from at least one of hydroxyethylpiperazine) and dithiobis (dibenzylamine). 27. The sulfur donor additional additive is 3,
3'-bis (trimethoxysilylpropyl) trisulfide and tetrasulfide; 3,3'-bis (triethoxysilylpropyl) trisulfide and tetrasulfide; 3,3'-bis (triethoxysilylethyltolylene) trisulfide And tetrasulfide; and the method of claim 1, selected from at least one of 3,3'-bis (trimethoxysilylethyltolylene) trisulfide and tetrasulfide. 28. In the organosilane polysulfide compound, the R ² group is an alkyl group, and the R ¹
The method of claim 1 wherein the group is selected from alkaryl, phenyl and haloaryl groups. 29. The alkyl group is methyl, ethyl or n.
-Propyl and n-decyl groups; the aralkyl group is selected from benzyl and alpha, alpha-dimethylbenzyl groups; the alkaryl group is p-
29. The method of claim 28, wherein the method is selected from tolyl and p-nonylphenol groups; and said haloaryl group is a p-chlorophenol group. 30. The organosilane disulfide of the organosilane polysulfide compound is: 2,2′-bis (trimethoxysilylethyl) disulfide; 3,3 ′
-Bis (trimethoxysilylpropyl) disulfide;
3,3'-bis (triethoxysilylpropyl) disulfide; 2,2'-bis (triethoxysilylpropyl) disulfide; 2,2'-bis (tripropoxysilylethyl) disulfide; 2,2'-bis (tri -S
ec-Butoxysilylethyl) disulfide; 3,3 '
-Bis (tri-t-butoxyethyl) disulfide; 3,
3'-bis (triethoxysilylethyltolylene) disulfide; 3,3'-bis (trimethoxysilylethyltolylene) disulfide; 3,3'-bis (triisopropoxypropyl) disulfide; 3,3'-bis (Trioctoxypropyl) disulfide; 2,2'-bis (2'-ethylhexoxysilylethyl) disulfide; 2,2'-bis (dimethoxyethoxysilylethyl) disulfide; 3,3'-bis (methoxyethoxypropoxy Silylpropyl) disulfide; 3,3'-
Bis (methoxydimethylsilylpropyl) disulfide; 3,3'-bis (cyclohexoxydimethylsilylpropyl) disulfide; 4,4'-bis (trimethoxysilylbutyl) disulfide; 3,3'-bis (trimethoxysilyl-3 -Methylpropyl) disulfide;
3,3'-bis (tripropoxysilyl-3-methylpropyl) disulfide; 3,3'-bis (dimethoxymethylsilyl-3-ethylpropyl) disulfide;
3'-bis (trimethoxysilyl-2-methylpropyl) disulfide; 3,3'-bis (dimethoxyphenylsilyl-2-methylpropyl) disulfide; 3,
3'-bis (trimethoxysilylcyclohexyl) disulfide; 12,12'-bis (trimethoxysilyldodecyl) disulfide; 12,12'-bis (triethoxysilyldodecyl) disulfide; 18,18'-bis (trimethoxysilyl) Octadecyl) disulfide;
18,18'-bis (methoxydimethylsilyloctadecyl) disulfide; 2,2'-bis (trimethoxysilyl-2-methylethyl) disulfide; 2,2'-bis (triethoxysilyl-2-methylethyl) disulfide; 2,2'-bis (tripropoxysilyl-2-methylethyl) disulfide; and at least one of 2,2'-bis (trioctoxysilyl-2-methylethyl) disulfide. Method. 31. The organosilane disulfide of the organosilane polysulfide compound is: 3,3′-bis (trimethoxysilylpropyl) disulfide; 3,
At least one of 3'-bis (triethoxysilylpropyl) disulfide; 3,3'-bis (triethoxysilylethyltrilene) disulfide; and 3,3'-bis (trimethoxysilylethyltrilene) disulfide
The method of claim 1, selected from the species. About 32. organosilane polysulfide, it is at least 95% of n is 2; an alkyl group above R ² group is selected from methyl, ethyl, n- propyl and n- decyl group; R ¹ above The method of claim 1, wherein the group is selected from benzyl, alpha, alpha-dimethylbenzyl group, p-tolyl, p-nonylphenol group and p-chlorophenol group. 33. The organosilane disulfide of the organosilane polysulfide compound is: 3,3′-bis (trimethoxysilylpropyl) disulfide;
At least one of 3'-bis (triethoxysilylpropyl) disulfide; 3,3'-bis (triethoxysilylethyltrilene) disulfide; and 3,3'-bis (trimethoxysilylethyltrilene) disulfide
33. The method of claim 32, selected from the species. 34. The organosilane disulfide of the organosilane polysulfide compound is: 3,3′-
Bis (trimethoxysilylpropyl) disulfide;
At least one of 3,3'-bis (triethoxysilylpropyl) disulfide; 3,3'-bis (triethoxysilylethyltrilene) disulfide; and 3,3'-bis (trimethoxysilylethyltrilene) disulfide CTAB of the above carbon black
A value of about 80 to about 150, a BET surface area of the silica, alumina and aluminosilicate of about 100 to about 300 m ² / g, a dibutyl phthalate (DBP) absorption value of about 150 to about 350 and a CTAB value of about 100 to About 22
0, and the pore size distribution by mercury porosimetry is:
Pore diameter of less than 5% is less than about 10 nm; 60-
90% of the pores have a diameter of about 10 to about 100 nm; 1
0-30% of the pores have a diameter of about 100 to about 1000 nm; and 5-20% of the pores have a diameter of about 1000 nm.
The sulfur donor additional additive comprises dimorpholine disulfide, dimorpholine tetrasulfide, tetramethylthiuram tetrasulfide, benzothiazyl-2, N-dithiomorpholide, thioplasts, dipentamethylene thiuram hexasulfide and disulfide caprolactam. The vulcanization accelerator for sulfur vulcanizable elastomer additional additive is selected from at least one mercaptobenzothiazole, tetramethylthiuram disulfide, benzothiazole disulfide, diphenylguanidine, zinc dithiocarbamate, alkylphenol disulfide, butylxanthogen. Zinc acid,
N-dicyclohexyl-2-benzothiazole sulfenamide, N-cyclohexyl-2-benzothiazole sulfenamide, N-oxydiethylenebenzothiazole-2-sulfenamide, N, N-diphenylthiourea, dithiocarbamylsulfene At least amide, N, N-diisopropylbenzothiazole-2-sulfenamide, zinc-2-mercaptotoluimidazole, dithiobis (N-methylpiperazine), dithiobis (N-betahydroxyethylpiperazine) and dithiobis (dibenzylamine) And the organosilane polysulfide additional additive is 3,
3'-bis (trimethoxysilylpropyl) trisulfide and tetrasulfide; 3,3'-bis (triethoxysilylpropyl) trisulfide and tetrasulfide; 3,3'-bis (triethoxysilylethyltolylene) trisulfide And tetrasulfide; and the method of claim 1, selected from at least one of 3,3'-bis (trimethoxysilylethyltolylene) trisulfide and tetrasulfide. 35. The manufactured rubber composition is heated to about 140.degree.
35. The method of claim 34, including the additional step of vulcanizing at about 190 ° C. 36. A rubber composition produced by the method of claim 35. 37. The method of claim 34, including the additional step of producing an assembly of a vulcanizable rubber tire and a tread comprising the rubber composition and vulcanizing the assembly at about 140 ° C to about 190 ° C. the method of. 38. A tire manufactured by the method of claim 37. 39. The method of claim 4, wherein for the vulcanizable elastomer, the conjugated diene is selected from isoprene and 1,3-butadiene and the vinyl aromatic compound is selected from styrene and alphamethylstyrene. 40. Sulfur vulcanizable elastomers are natural and synthetic cis 1,4-polyisoprene rubbers, styrene / butadiene copolymer rubbers produced by emulsion polymerization,
Styrene / butadiene copolymer rubber produced by organic solution polymerization, 3,4-polyisoprene rubber, isoprene / butadiene rubber, styrene / isoprene / butadiene terpolymer rubber, cis 1,4-polybutadiene rubber, emulsion polymerization The method of claim 4 selected from at least one of a styrene / butadiene / acrylonitrile terpolymer rubber and a butadiene / acrylonitrile copolymer rubber produced. 41. The silica has a BET surface area of about 100-.
About 300 m ² / g, dibutyl phthalate (DBP) absorption value about 150 to about 350, CTAB value about 100 to about 2.
20 and the pore size distribution by mercury porosimetry: less than 5%, the diameter of the pores is less than about 10 nm; 6
0 to 90% of the pore diameters are about 10 to about 100 nm; 10 to 30% of the pore diameters are about 100 to about 1000.
nm; and 5-20% pore diameter is about 100 nm.
Method according to claim 4, characterized in that it is greater than 0 nm. 42. The filler is about 15 to about 100% by weight.
Of precipitated silica, and correspondingly about 5 to about 85% by weight of carbon black;
42. The method of claim 41, having a CTAB value of about 150. 43. The method of claim 42, wherein the filler comprises about 60 to about 95 wt% silica, and correspondingly about 40 to about 5 wt% carbon black. 44. The filler is about 15 to about 100% by weight.
Alumina, and correspondingly about 5 to about 85% by weight of carbon black;
It has a CTAB value of about 150 and the alumina is about 100.
Pore size distribution by mercury porosimetry having a CTAB value of from about 220 to about 220: less than about 5% of pores has a diameter of less than about 10 nm;
The method of claim 4, wherein 0 to about 100 nm; 10 to 30% of the pores have a diameter of about 100 to about 1000 nm; and 5 to 20% of the pores have a diameter of greater than about 1000 nm. 45. The method of claim 44, wherein the filler comprises about 60 to about 95 wt% alumina, and correspondingly about 40 to about 5 wt% carbon black. 46. The filler is about 15 to about 100% by weight.
Aluminosilicates, and correspondingly from about 5 to about 85% by weight of carbon black; said carbon black having a CTAB value of from about 80 to about 150 and said aluminosilicate having a CTAB value of from about 100 to about 220. Have,
And the pore size distribution by mercury porosimetry is: 5%
The diameter of the pores of less than about 10 nm; 60-90
% Pore diameter is about 10 to about 100 nm; 10 to
The method of claim 4, wherein 30% of the pore diameters are about 100 to about 1000 nm; and 5 to 20% of the pore diameters are greater than about 1000 nm. 47. The method of claim 46, wherein the filler comprises about 60 to about 95 wt% aluminosilicate, and correspondingly about 40 to about 5 wt% carbon black. 48. A combination of (a) a natural aluminosilicate selected from muscovite, beryl, dichroite, sepiolite and kaolinite and (b) a basic solution or mixture of (i) silicate and aluminate. by precipitation or (ii) is selected from at least one synthetic aluminosilicates prepared by chemical reaction between silanols and NaAlO ₂ of silicon dioxide, the method of claim 46. 49. The method of claim 48, wherein for the synthetic aluminosilicate, about 5 to about 95% of its surface comprises silica moieties, and correspondingly about 95 to about 5% of its surface comprises aluminum moieties. 50. The synthetic aluminosilicate has the formula:
[(Al ₂ O ₃ ) _x · (SiO ₂ ) _y · (H ₂ O) _z ];
_{[(Al 2 O 3) x} · (SiO 2) y · MO] ( wherein, M is a is magnesium or calcium) represented by the method of claim 46. 51. The additional additive of sulfur donor is selected from at least one of dimorpholine tetrasulfide, tetramethylthiuram tetrasulfide, benzothiazyl-2, N-dithiomorpholide, thioplasts, dipentamethylene thiuram hexasulfide and disulfide caprolactam. The method of claim 4, which is selected. 52. The vulcanization accelerator for a vulcanizable elastomer additional additive is mercaptobenzothiazole, tetramethylthiuram disulfide, benzothiazole disulfide, diphenylguanidine, zinc dithiocarbamate, alkylphenol disulfide, zinc butylxanthogenate, N-dicyclohexyl-2-benzothiazole sulfenamide, N-cyclohexyl-2-
Benzothiazole sulfenamide, N-oxydiethylene benzothiazole-2-sulfenamide, N, N
-Diphenylthiourea, dithiocarbamylsulfenamide, N, N-diisopropylbenzothiazole-2-
5. The method of claim 4, wherein the method is selected from at least one of sulfenamide, zinc-2-mercaptotoluimidazole, dithiobis (N-methylpiperazine), dithiobis (N-betahydroxyethylpiperazine) and dithiobis (dibenzylamine). . 53. The additive of the sulfur donor is 3,
3'-bis (trimethoxysilylpropyl) trisulfide and tetrasulfide; 3,3'-bis (triethoxysilylpropyl) trisulfide and tetrasulfide; 3,3'-bis (triethoxysilylethyltolylene) trisulfide And tetrasulfide; and the method of claim 4, selected from at least one of 3,3'-bis (trimethoxysilylethyltolylene) trisulfide and tetrasulfide. 54. In the organosilane polysulfide compound, the R ² group is an alkyl group, and the R ¹
The method of claim 4, wherein the group is selected from alkaryl, phenyl and haloaryl groups. 55. The alkyl group is methyl, ethyl or n.
-Propyl and n-decyl groups; the aralkyl group is selected from benzyl and alpha, alpha-dimethylbenzyl groups; the alkaryl group is p-
55. The method of claim 54, wherein the method is selected from tolyl and p-nonylphenol groups; and said haloaryl group is a p-chlorophenol group. 56. The organosilane disulfide of the organosilane polysulfide compound is: 2,2′-bis (trimethoxysilylethyl) disulfide; 3,3 ′
-Bis (trimethoxysilylpropyl) disulfide;
3,3'-bis (triethoxysilylpropyl) disulfide; 2,2'-bis (triethoxysilylpropyl) disulfide; 2,2'-bis (tripropoxysilylethyl) disulfide; 2,2'-bis (tri -S
ec-Butoxysilylethyl) disulfide; 3,3 '
-Bis (tri-t-butoxyethyl) disulfide; 3,
3'-bis (triethoxysilylethyltolylene) disulfide; 3,3'-bis (trimethoxysilylethyltolylene) disulfide; 3,3'-bis (triisopropoxypropyl) disulfide; 3,3'-bis (Trioctoxypropyl) disulfide; 2,2'-bis (2'-ethylhexoxysilylethyl) disulfide; 2,2'-bis (dimethoxyethoxysilylethyl) disulfide; 3,3'-bis (methoxyethoxypropoxy Silylpropyl) disulfide; 3,3'-
Bis (methoxydimethylsilylpropyl) disulfide; 3,3'-bis (cyclohexoxydimethylsilylpropyl) disulfide; 4,4'-bis (trimethoxysilylbutyl) disulfide; 3,3'-bis (trimethoxysilyl-3 -Methylpropyl) disulfide;
3,3'-bis (tripropoxysilyl-3-methylpropyl) disulfide; 3,3'-bis (dimethoxymethylsilyl-3-ethylpropyl) disulfide;
3'-bis (trimethoxysilyl-2-methylpropyl) disulfide; 3,3'-bis (dimethoxyphenylsilyl-2-methylpropyl) disulfide; 3,
3'-bis (trimethoxysilylcyclohexyl) disulfide; 12,12'-bis (trimethoxysilyldodecyl) disulfide; 12,12'-bis (triethoxysilyldodecyl) disulfide; 18,18'-bis (trimethoxysilyl) Octadecyl) disulfide;
18,18'-bis (methoxydimethylsilyloctadecyl) disulfide; 2,2'-bis (trimethoxysilyl-2-methylethyl) disulfide; 2,2'-bis (triethoxysilyl-2-methylethyl) disulfide; The compound according to claim 4, which is selected from at least one of 2,2'-bis (tripropoxysilyl-2-methylethyl) disulfide; and 2,2'-bis (trioctoxysilyl-2-methylethyl) disulfide. Method. 57. The organosilane disulfide of the organosilane polysulfide compound is: 3,3′-bis (trimethoxysilylpropyl) disulfide; 3,
At least one of 3'-bis (triethoxysilylpropyl) disulfide; 3,3'-bis (triethoxysilylethyltrilene) disulfide; and 3,3'-bis (trimethoxysilylethyltrilene) disulfide
The method of claim 4, selected from the species. 58. For the organosilane polysulfide compound, at least 95% of n is 2; the R ² group is an alkyl group selected from methyl, ethyl, n-propyl and n-decyl groups; ¹ group is benzyl, alpha, alpha-dimethylbenzyl group, p
-The method of claim 4 selected from tolyl, p-nonylphenol and p-chlorophenol groups. 59. The organosilane disulfide of the organosilane polysulfide compound is: 3,3′-bis (trimethoxysilylpropyl) disulfide; 3,
At least one of 3'-bis (triethoxysilylpropyl) disulfide; 3,3'-bis (triethoxysilylethyltrilene) disulfide; and 3,3'-bis (trimethoxysilylethyltrilene) disulfide
59. The method of claim 58, selected from the species. 60. The organosilane disulfide of the organosilane polysulfide compound is: 3,3′-
Bis (trimethoxysilylpropyl) disulfide;
At least one of 3,3'-bis (triethoxysilylpropyl) disulfide; 3,3'-bis (triethoxysilylethyltrilene) disulfide; and 3,3'-bis (trimethoxysilylethyltrilene) disulfide CTAB of the above carbon black
A value of about 80 to about 150, a BET surface area of the silica, alumina and aluminosilicate of about 100 to about 300 m ² / g, a dibutyl phthalate (DBP) absorption value of about 150 to about 350 and a CTAB value of about 100 to About 22
0, and the pore size distribution by mercury porosimetry is:
Pore diameter of less than 5% is less than about 10 nm; 60-
90% of the pores have a diameter of about 10 to about 100 nm; 1
0-30% of the pores have a diameter of about 100 to about 1000 nm; and 5-20% of the pores have a diameter of about 1000 nm.
The sulfur donor additional additive comprises dimorpholine disulfide, dimorpholine tetrasulfide, tetramethylthiuram tetrasulfide, benzothiazyl-2, N-dithiomorpholide, thioplasts, dipentamethylene thiuram hexasulfide and disulfide caprolactam. Selected from at least one; said vulcanization accelerator for vulcanizable elastomer additional additive,
Mercaptobenzothiazole, tetramethylthiuram disulfide, benzothiazole disulfide, diphenylguanidine, zinc dithiocarbamate, alkylphenol disulfide, zinc butylxanthate, N-
Dicyclohexyl-2-benzothiazole sulfenamide, N-cyclohexyl-2-benzothiazole sulfenamide, N-oxydiethylenebenzothiazole-2-sulfenamide, N, N-diphenylthiourea, dithiocarbamylsulfenamide, N, N-diisopropylbenzothiazole-2-sulfenamide,
Zinc-2-mercaptotoluimidazole, dithiobis (N-methylpiperazine), dithiobis (N-betahydroxyethylpiperazine) and dithiobis (dibenzylamine), and the organosilane polysulfide additional additive; Three
3'-bis (trimethoxysilylpropyl) trisulfide and tetrasulfide; 3,3'-bis (triethoxysilylpropyl) trisulfide and tetrasulfide; 3,3'-bis (triethoxysilylethyltolylene) trisulfide And tetrasulfide; and the method of claim 4, selected from at least one of 3,3'-bis (trimethoxysilylethyltolylene) trisulfide and tetrasulfide. 61. The rubber composition produced is heated to about 140.degree.
The method of claim 4 including the additional step of vulcanizing at about 190 ° C. 62. A vulcanized rubber composition produced by the method of claim 61. 63. The method of claim 60, comprising the additional step of producing an assembly of a vulcanizable rubber tire and a tread comprising the rubber composition and vulcanizing the assembly at about 140 ° C to about 190 ° C. the method of. 64. Manufactured by the method of claim 63,
Vulcanized rubber tire. 65. The above-mentioned organosilane compound,
61. The method of claim 60, wherein at least 95% of n is 2. 66. The manufactured rubber composition is heated to about 140.degree.
66. The method of claim 65, including the additional step of vulcanizing at about 190 ° C. 67. Manufactured by the method of claim 66,
Vulcanized rubber composition. 68. The method of claim 65, including the additional step of producing an assembly of a vulcanizable rubber tire and a tread comprising the rubber composition and vulcanizing the assembly at about 140 ° C to about 190 ° C. the method of. 69. Manufactured by the method of claim 68,
Vulcanized rubber tire. 70. The preliminary step (A) comprises adding the elastomer, the particulate filler and the organosilane polysulfide compound to one or more of the sequential mixing steps, and the sulfur source and / or vulcanization accelerator. The method of claim 4, comprising at least two sequential mixing steps, wherein is added to the subsequent premixing step. 71. The preliminary step (A) comprises about 20 to about 6.
At least 2% by weight of silica, said organosilane disulfide compound and said sulfur source and / or vulcanization accelerator are added to one or more mixing steps, and the remainder thereof is added to at least one subsequent premixing step, at least 2
The method of claim 4, comprising one sequential mixing step. 72. The organosilane polysulfide compound wherein at least 80% of n is 2 is from about 25 to about 7.
5% by weight of the above organosilane polysulfide compound,
The method of claim 1, wherein the thermomechanical premixing step is added in the form of granules, and correspondingly, containing from about 75 to about 25% by weight of particulate carbon black. 73. At least 80% of the organosilane polysulfide compound wherein n is 2 is from about 25 to about 7.
5% by weight of the above organosilane polysulfide compound,
The method of claim 4, wherein the thermomechanical premix is added in the form of granules, and correspondingly containing from about 75 to about 25% by weight of particulate carbon black. 74. At least 80% of the organosilane polysulfide compound wherein n is 2 is from about 25 to about 7.
5% by weight of the above organosilane polysulfide compound,
61. The method of claim 60, wherein the thermomechanical premix is added in the form of granules, and correspondingly containing from about 75 to about 25% by weight of particulate carbon black. 75. At least 95% of the organosilane polysulfide compound wherein n is 2 is from about 25 to about 7.
5% by weight of the above organosilane polysulfide compound,
61. The method of claim 60, wherein the thermomechanical premix is added in the form of granules, and correspondingly containing from about 75 to about 25% by weight of particulate carbon black. 76. An additional step of producing an assembly of a sulfur vulcanizable rubber tire and a tread comprising the rubber composition and vulcanizing the assembly at about 140 ° C to about 190 ° C; and at least 80% of an organosilane polysulfide compound having an n of 2 in the form of a granulate comprising about 40 to about 60% by weight of the above organosilane polysulfide compound and correspondingly about 60 to about 40% by weight of particulate carbon black. 61. The method of claim 60, further comprising: adding to the thermomechanical premix.